EP3453689B1 - Réfractaire électrofondu à forte teneur en zircone et son procédé de fabrication - Google Patents

Réfractaire électrofondu à forte teneur en zircone et son procédé de fabrication Download PDF

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EP3453689B1
EP3453689B1 EP18192492.9A EP18192492A EP3453689B1 EP 3453689 B1 EP3453689 B1 EP 3453689B1 EP 18192492 A EP18192492 A EP 18192492A EP 3453689 B1 EP3453689 B1 EP 3453689B1
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refractory
mass
zirconia electrocast
zirconia
cracks
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EP3453689A1 (fr
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Kenji Matano
Nobuo Tomura
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AGC Ceramics Co Ltd
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AGC Ceramics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/484—Refractories by fusion casting
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/05—Refractories by fusion casting
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • C04B35/657—Processes involving a melting step for manufacturing refractories
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

  • the present invention relates to a high-zirconia electrocast refractory according to claim 1 and, in particular, to a high-zirconia electrocast refractory suitable for use for a glass melting furnace being a glass manufacturing furnace
  • a high-zirconia electrocast refractory containing 80 mass% or more of ZrO 2 as a chemical component has been conventionally used as a refractory for a glass melting furnace.
  • the high-zirconia electrocast refractory has high corrosion resistance and low staining properties with respect to molten glass, and is frequently used for a portion in contact with the molten glass of the glass melting furnace.
  • Such a high-zirconia electrocast refractory is composed of a large amount of zirconia crystal grains and a small amount of matrix glass filling spaces among the crystal grains.
  • the present inventors have found that a high-zirconia electrocast refractory containing 96.5 to 98.5 mass% of ZrO 2 , 0.8 to 2.7 mass% of SiO 2 , 0.04 to 0.35 mass% of Na 2 O and K 2 O in total, 0.02 to 0.18 mass% of B 2 O 3 , in terms of oxide, as a chemical composition, the contents of Na 2 O, K 2 O, and B 2 O 3 satisfying a predetermined relation may contain Al 2 O 3 and can solve the above problem of enabling suppression of occurrence of cracks in manufacturing the same and preventing occurrence of cracks in use for the furnace material while having extremely high corrosion resistance to the molten glass (refer to Patent Reference 5).
  • a high-zirconia electrocast refractory of the present invention contains 96.7 to 98.5 mass% of ZrO 2 , 0.8 to 2.7 mass% of SiO 2 , 0.1 to 0.4 mass% of Al 2 O 3 , 0 to 0.2 mass% of Na 2 O, and 0.21 to 1 mass% of K 2 O, and does not substantially contain B 2 O 3 , in terms of oxide, as a chemical composition, wherein contents of the Na 2 O and the K 2 O satisfy a relation of following Formula (1) 0.15 mass % ⁇ C K 2 O / 2 + C Na 2 O ⁇ 0.6 mass % where C K2O is the content of K 2 O and C Na2O is the content of Na 2 O, and each of the contents is expressed by mass% in the refractory.
  • the content of ZrO 2 is high, and therefore high corrosion resistance is exhibited to the molten glass, and the contents of components other than the ZrO 2 component are optimized, and therefore occurrence of cracks can be suppressed in manufacturing a large-size high-zirconia electrocast refractory, and the residual expansion of the refractory can be made small.
  • the content of SiO 2 is 0.8 to 2.7 mass% in the high-zirconia electrocast refractory.
  • the high-zirconia electrocast refractory containing 0.8 mass% or more of SiO 2 can mitigate the thermal stress with respect to the temperature change in manufacture and prevent cracks.
  • a content of more than 2.7 mass% the percentage of SiO 2 in the matrix glass becomes high and the viscosity of the matrix glass increases, possibly causing cracks to occur in manufacturing the refractory.
  • the content of SiO 2 is preferably 1 to 2.4 mass% and more preferably 1.2 to 2.1 mass%.
  • these Na 2 O and K 2 O are compounded so that the contents of Na 2 O and K 2 O in the high-zirconia electrocast refractory satisfy the relation of following Formula (1) 0.15 mass % ⁇ C K 2 O / 2 + C Na 2 O ⁇ 0.6 mass % where C K2O is the content of K 2 O and C Na2O is the content of Na 2 O, and each of the contents is expressed by mass% in the refractory.
  • the [(C K2O /2 + C Na2O )/C SiO2 ] is preferably 0.09 to 0.3, and more preferably 0.12 to 0.27.
  • Na 2 O, K 2 O, and SiO 2 it is preferable that the contents of Na 2 O, K 2 O, and SiO 2 in the high-zirconia electrocast refractory satisfy the relation of following Formula (3) 0.11 ⁇ C K 2 O / 1.5 + C Na 2 O / C SiO 2 ⁇ 0.5 where C Na2O is the content of Na 2 O, C K2O is the content of K 2 O, and C SiO2 is the content of SiO 2 , and each of the contents is expressed by mass% in the refractory.
  • the ratio between Na 2 O and K 2 O (C K2O /C Na2O ) is 2 or more, it is possible to effectively suppress occurrence of cracks and increase in residual expansion of the refractory.
  • This ratio (C K2O /C Na2O ) is preferably 2 to 11 and more preferably 3.5 to 8. More specifically, the residual volume expansion rate of the high-zirconia electrocast refractory to be manufactured can be made 20% or less, which is preferable in terms of being able to effectively suppress occurrence of cracks when it is used as the furnace material of the glass furnace.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
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  • Structural Engineering (AREA)
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  • General Engineering & Computer Science (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Claims (5)

  1. Réfractaire électrofondu à forte teneur en zircone, contenant 96,7 à 98,5 % en masse de ZrO2, 0,8 à 2,7 % en masse de SiO2, 0,1 à 0,4 % en masse de Al2O3, 0 à 0,2 % en masse de Na2O et 0,21 à 1 % en masse de K2O, et 0,01 % en masse ou moins de B2O3, en termes d'oxyde, sous la forme d'une composition chimique, dans lequel les teneurs en Na2O et en K2O satisfont à une relation de Formule (1) suivante 0,15 % en masse ≤ C K 2 O / 2 + C Na 2 O ≤ 0,6 % en masse
    Figure imgb0010
     où CK2O est la teneur en K2O et CNa2O est la teneur en Na2O, et chacune des teneurs est exprimée en % en masse dans le réfractaire, et
    dans lequel un rapport CK2O sur CNa2O (CK2O/CNa2O) est de 2 ou plus.
  2. Réfractaire électrofondu à forte teneur en zircone selon la revendication 1, dans lequel les teneurs en Na2O, en K2O et en SiO2 satisfont à une relation de Formule (2) suivante 0,09 ≤ C K 2 O / 2 + C Na 2 O / C SiO 2 ≤ 0,4
    Figure imgb0011
     où CK2O est la teneur en K2O, CNa2O est la teneur en Na2O et CSiO2 est la teneur en SiO2, et chacune des teneurs est exprimée en % en masse dans le réfractaire.
  3. Réfractaire électrofondu à forte teneur en zircone selon la revendication 1 ou 2, dans lequel une densité apparente est de 5,4 ou plus.
  4. Réfractaire électrofondu à forte teneur en zircone selon l'une quelconque des revendications 1 à 3, dans lequel une porosité est de 1,5 % ou moins.
  5. Réfractaire électrofondu à forte teneur en zircone selon l'une quelconque des revendications 1 à 4, dans lequel une masse de celui-ci est de 200 kg ou plus.
EP18192492.9A 2017-09-08 2018-09-04 Réfractaire électrofondu à forte teneur en zircone et son procédé de fabrication Active EP3453689B1 (fr)

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JP2017172924 2017-09-08
JP2018138361A JP7099898B2 (ja) 2017-09-08 2018-07-24 高ジルコニア質電鋳耐火物及びその製造方法

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EP3453689A1 EP3453689A1 (fr) 2019-03-13
EP3453689B1 true EP3453689B1 (fr) 2020-08-26

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EP4253347A4 (fr) * 2020-11-24 2024-11-06 Saint Gobain Tm K K Matériau réfractaire coulé électrofondu à haute teneur en zircone

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CN109467447A (zh) 2019-03-15
CN109467447B (zh) 2022-12-27
US10815155B2 (en) 2020-10-27
EP3453689A1 (fr) 2019-03-13
US20190077714A1 (en) 2019-03-14

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